1. Field of the Invention
The present invention relates to N-substituted pyridinylidene compounds, to the enantiomers, diastereomers, derivatives and salts thereof and to compositions comprising such compounds. The invention also relates to the use of the N-substituted pyridinylidene compounds, of their salts or of compositions comprising them for combating animal pests. Furthermore the invention relates also to methods of applying such compounds.
Animal pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
It is therefore an object of the present invention to provide compounds having a good pesticidal activity, especially against difficult to control insects and acaridae.
It has been found that these objects are solved by N-substituted pyridinylidene derivatives of the general formula I:
N-substituted pyridinylidene compounds of the general formula (I):
wherein                X is selected from O, S, or NR5;        Het is a 5 or 6 membered carbon-bound or optionally nitrogen-bound heterocyclic or heteroaromatic ring system, each ring members selected from carbon atoms and at least one, up to three heteroatoms independently selected from sulfur, oxygen or nitrogen, wherein the carbon, oxygen and nitrogen ring members can independently be partly or fully oxidized, and wherein each ring of the ring system is optionally substituted by k substituents selected from R6a, wherein k is an integer selected from 1, 2, 3, 4, or 5, and two or more substituents R6a are selected independently from one another;        R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, cyano, nitro, —SCN, C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, wherein each of the aforementioned carbon chain radicals are unsubstituted, partly or completely halogenated or may carry any combination of one or more radicals R7, Si(R11)2R12, OR16, OSO2R16, S(O)nR16, S(O)nNR17aR17b, NR17aR17b, C(═O)NR17aR17b, C(═S)NR17aR17b, C(═O)OR16, C(═O)R15, C(═S)R15, phenyl, optionally substituted with one or more, e.g. 1, 2, 3, 4 or 5 substituents R18, which are independently selected from one another,                    a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3 or 4, substituents R18, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,            or            R1 and R2 from, together with the carbon atom, which they attached to, a 3- to 6-membered saturated or partly unsaturated carbocyclic or heterocyclic ring, wherein each of the carbon atoms of said cycle are unsubstituted or may carry any combination of 1 or 2 radicals R7,            or            R1 and R2 may together be ═O, ═CR13R14; ═S; ═S(O)nR16; ═S(O)nNR17aR17b, ═NR17a, ═NOR16; ═NNR17a;                        R3 is selected from hydrogen, halogen, cyano, SCN, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C3-C8-cycloalkyl, C2-C6-alkenyl, C2-C6-alkinyl, wherein each of the eight last mentioned carbon chain radicals are unsubstituted, partly or completely halogenated or may carry any combination of one or more radicals R7;                    OR8, OSO2R8, S(O)nR8, S(O)nNR9aR9b, NR9aR9b, C(═O)NR9aR9b, C(═S)NR9aR9b, C(═O)R7, C(═S)R7,            phenyl, optionally substituted with one or more, e.g. 1, 2, 3, 4 or 5 substituents R10, which are independently selected from one another,            a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3 or 4 substituents R18, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;                        R4 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, wherein each of the six last mentioned carbon chain radicals are unsubstituted, partly or completely halogenated or may carry any combination of one or more radicals R7,                    Si(R11)2R12, OR16, OSO2R16, S(O)nR16, S(O)nNR17aR17b, NR17aR17b, C(═O)NR17aR17b, C(═S)NR17aR17b, C(═O)OR16, C(═O)R15, C(═S)R15, phenyl, optionally substituted with 1, 2, 3, 4 or 5 substituents R18, which are independently selected from one another,            a 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with one or more, e.g. 1, 2, 3 or 4, substituents R10, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;                        R5 is selected from the group consisting of hydrogen, cyano, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from R7,                    phenyl, benzyl, pyridyl, pyrimidyl, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1, 2 or 3 substituents selected from C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy or (C1-C6-alkoxy)carbonyl,                        R6, R6a are each, independently from the number of R6 or R6a present and independently from one another, selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, SCN, SF5, C1-C10-alkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkinyl, and wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals may optionally be further substituted independently from one another with one or more R7,                    OR8, NR9aR9b, S(O)nR8, S(O)nNR9aR9b, C(═O)R7, C(═O)NR9aR9b, C(═O)OR8, C(═S)R7, C(═S)NR9aR9b, C(═S)OR8, C(═S)SR8, C(═NR9a)R7, C(═NR9a)NR9aR9b, Si(R11)2R12;            phenyl, optionally substituted with 1, 2, 3, 4 or 5 substituents selected independently from R10;            a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3, 4 or 5 substituents selected independently from R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;            or two of R6 or two of R6a present on one ring carbon or sulfur atom may together form ═O, ═CR13R14; ═S; ═S(O)nR16; ═S(O)nNR17aR17b, ═NR17a, ═NOR16; ═NNR17a;            or two R6 together form a C2-C7 alkylene chain, thus forming, together with the ring atom(s) to which they are bound, a 3-, 4-, 5-, 6-, 7- or 8-membered ring, where the alkylene chain may be interrupted by 1 or 2 O, S and/or NR17a and/or 1 or 2 of the CH2 groups of the alkylene chain may be replaced by a group C═O, C═S and/or C═NR17a; and/or the alkylene chain may be substituted by one or more radicals selected from the group consisting of halogen, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl which may be substituted by one or more, e.g. 1, 2, 3, 4 or 5 radicals R10, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R18;                        R7 is each independently from one another selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, —SCN, SF5, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkinyl, C2-C6 haloalkinyl, Si(R11)2R12; OR16, OSO2R16, S(O)nR16, S(O)nNR17aR17b, NR17aR17b, C(═O)NR17aR17b, C(═S)NR17aR17b; C(═O)OR16, C(═O)R15, C(═S)R15, C(═NR17a)R15,                    phenyl, optionally substituted with 1, 2, 3, 4 or 5 substituents R10, which are independently selected from one another,            a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3 or 4 substituents R10, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,            or            two R7 present on one carbon atom may together form ═O, ═CR13R14; ═S; ═S(O)nR16; ═S(O)nNR17aR17b, ═NR17a, ═NOR16; ═NNR17a;            or            two R7 may form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partly unsaturated carbocyclic or heterocyclic ring together with the carbon atoms to which the two R7 are bonded to;                        R8 is each independently from one another selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, C3-C8-cycloalkyl, C4-C8-alkylcycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkinyl, C2-C6 haloalkinyl, —Si(R11)2R12, S(O)nR16, S(O)nNR17aR17b, NR17aR17b, —N═CR13R14, —C(═O)R15, C(═O)NR17aR17b, C(═S)NR17aR17b, C(═O)OR16, phenyl, optionally substituted with one or more substituents R10; which are selected independently from one another,                    a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3 or 4 substituents R10, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;                        R9a, R9b are each independently from one another selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkinyl, C2-C6 haloalkinyl, S(O)nR16, —S(O)nNR17aR17b, C(═O)R15, C(═0)OR16, C(═O)NR17aR17b, C(═S)R15, C(═S)SR16, C(═S)NR17aR17b, C(═NR17a)R18;                    phenyl, optionally substituted with one or more, e.g. 1, 2, 3 or 4, substituents R10, which are selected independently from one another;            a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with 1, 2, 3 or 4 substituents R10, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;            or,            R9a and R9b are together a C2-C7 alkylene chain and form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partly saturated or unsaturated aromatic ring together with the nitrogen atom they are bonded to, wherein the alkylene chain may contain one or two heteroatoms selected from oxygen, sulfur or nitrogen, and may optionally be substituted with halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkinyl, C2-C6 haloalkinyl,                            phenyl, optionally substituted with one or more substituents R10; which are selected independently from one another, a 3-, 4-, 5-, 6-, or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with one or more substituents R10, selected independently from one another, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;                                    or            R9a and R9b together may form a═CR13R14, ═S(O)nR16, ═S(O)nNR17R17, ═NR17 or ═NOR16 radical;                        R10 is each independently from one another selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, SCN, SF5, C1-C10-alkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkinyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals may optionally be substituted with one or more R15, which are selected independently from one another,                    Si(R11)2R12, OR16, OS(O)nR16, —S(O)nR16, S(O)nNR17aR17b, NR17aR17b, C(═O)R15, C(═S)R15, C(═O)OR16, —C(═NR17a)R15, C(═O)NR17aR17b, C(═S)NR17aR17b, phenyl, optionally substituted with halogen, cyano, nitro, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy,            a 3-, 4-, 5-, 6- or 7-membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and/or sulfur, optionally substituted with one or more substituents selected independently from one another from halogen, cyano, NO2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;            or            two R10 present together on one atom of a partly saturated heterocyclic may be ═O, ═CR13R14; ═S(O)nR16; ═S(O)nNR17aR17b, ═NR17a, ═NOR16 or ═NNR17a;            or,            two R10 on adjacent carbon atoms may be a bridge selected from CH2CH2CH2CH2, CH═CH—CH═CH, N═CH—CH═CH, CH═N—CH═CH, N═CH—N═CH, OCH2CH2CH2, OCH═CHCH2, CH2OCH2CH2, OCH2CH2O, OCH2OCH2, CH2CH2CH2, CH═CHCH2, CH2CH2O, CH═CHO, CH2OCH2, CH2C(═O)O, C(═O)OCH2, O(CH2)O, SCH2CH2CH2, SCH═CHCH2, CH2SCH2CH2, SCH2CH2S, SCH2SCH2, CH2CH2S, CH═CHS, CH2SCH2, CH2C(═S)S, C(═S)SCH2, S(CH2)S, CH2CH2NR17a, CH2CH═N, CH═CH—NR17a, OCH═N, SCH═N and form together with the carbon atoms to which the two R10 are bonded to a 5-membered or 6-membered partly saturated or unsaturated, aromatic carbocyclic or heterocyclic ring, wherein the ring may optionally be substituted with one or two substituents selected from ═O, OH, CH3, OCH3, halogen, cyano, halomethyl or halomethoxy;                        R11, R12 (are each independently from one another selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkoxyalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkinyl, C2-C6 haloalkinyl, C3-C8 cycloalkyl, C3-C5 halocycloalkyl, C1-C6 alkoxyalkyl, C1-C6 haloalkoxyalkyl and phenyl, optionally substituted with one or more substituents R18; which are selected independently from one another;        R13, R14 are each independently from one another selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C6 cycloalkyl, C1-C4 alkoxyalkyl, phenyl and benzyl;        R15 is each independently from one another selected from the group consisting of hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tenbutyldimethylsilyl,                    C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxgenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;            phenyl, benzyl, pyridyl, phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or to carry 1, 2 or 3 substituents selected from C1-C6-alkyl, C1-C6-alkoxy, C1-C6 haloalkoxy, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)amino or di-(C1-C6-alkyl)amino,            or            two R15 present on the same carbon atom may together be ═O, ═CH(C1-C4), ═C(C1-C4-alkyl)C1-C4-alkyl, ═N(C1-C6-alkyl) or ═NO(C1-C6-alkyl);                        R16 is each independently from one another selected from the group consisting of hydrogen, cyano, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tertbutyldimethylsilyl,                    C1-C6-alkyl, C2-C6-alkenyl, C3-C8-cycloalkyl, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,            phenyl, benzyl, pyridyl, phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1, 2 or 3 substituents selected from C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy or (C1-C6-alkoxy)carbonyl;                        R17a, R17b are each independently from one another selected from the group consisting of hydrogen, cyano, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio,                    C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tenbutyldimethylsilyl, C1-C6-alkyl, C2-C6-alkenyl, C3-C8-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4-alkoxy,            phenyl, benzyl, pyridyl, phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1, 2 or 3 substituents selected from C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy or (C1-C6-alkoxy)carbonyl,            or,            R17a and R17b may together be a C2-C5 alkylene chain forming a 3- to 7-membered saturated, partly saturated or unsaturated ring together with the nitrogen atom R17a and R17b are bonded to, wherein the alkylene chain may contain 1 or 2 heteroatoms selected from oxygen, sulfur or nitrogen, and may optionally be substituted with halogen, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;                        n is an integer selected independently from one another from 0, 1 or 2;        and/or an enantiomer, diastereomer, E/Z-isomer or agriculturally or veterinarily acceptable salts thereof for controlling and/or combating animal pests.        
2. Description of Related Art
Certain heteroarylalkyl-substituted 5- and 6-membered heterocycles and their use as insecticide have been described in DE 3639877.
Nitromethyl)pyridinium compounds and their insecticidal activity are disclosed in DE 2416350. The preparation of (N-heterocyclylimino)heterocyclic compounds as insecticides is disclosed in WO 9215564.
Benzoyl substituted like the compound S24795 have been disclosed as alpha-7 Nicotinic Receptor Interactors in Journal of Neuroscience 2009), 29(35), 10961-10973.
Substituted pyridinylidene carbonyl compounds and their chemistry are described in Journal of the Chemical Society [Section] 1967, 167(10), 983-988, Journal of the Chemical Society 1965, 3093-3096, Australian Journal of Chemistry 1972, 5(7), 1549-1560 and Khimiya Geterotsiklich-eskikh Soedinenii 1991 (8), 1110-1116. Pyridine-imine compounds and methods for producing them are described in WO2012/029672 and WO/2013/031671.